Method of cross-dyeing fabrics



is Patented .lu ne res "PATENT-'5 orrlcs ARTHUR. s. ROBERTS, or HENDEBSONVILLE, NO TH CAROLINA METHOD or cRoss-nyrgmo FABRICS No Drawing. 7 Application filed April 6, 1928, Serial No. 268,073. Renewed December 11, 1930.

This invention relates to newcross-dyedfabrics and to methods of preparing the same.

This application is in part a continuation of my co-pending applications 240,919, 240,- 920 and 240,921.

According to this invention, fabrics comprising cotton fibers and fibers of a regenerted cellulose, particularly viscose silk, are cross-dyed so that the cotton and regenerated cellulose fibers are dyed diflerent colors. It has heretofore been claimed by those skilled in the art of dyeing fabrics that afabric composed of cotton and xant-hate silk, i. e.,

viscose silk, cannot be dyed in any other manner than that of dyeing both the cotton and the xanthate silk or viscose silk of the same color, due to the fact that cotton and viscose silk have the same afiinity for dyes. 4

It is the purpose of this invention to'set forth a method whereby cotton and viscose silk or xanthatesilk, can be dyed different colors when woven in the same fabric, and by dyeing each fiber in a separate dye-bath,

or by combining the two dye-baths and dyeing two separate and distinct colors atone and the same "operation, the art of which is known as cross-dyeing. I am aware that the art of cross-dyeing has beenused here'- tofore for various textile articles woven of different materials, but, as stated, there has not heretofore been used any method whereby cotton and regenerated cellulose of the viscose type, when woven in the same fabric can be dyed separate and distinct colors either by separate dyeing or by one operation. s

The cross-dyed fabrics of the present in- Vention are dyed in the piece and differ from materials which are manufactured from fibers which have previously been dyed. The new cross-dyed fabrics comprise cotton fibers and fibers of a regenerated cellulose, and the dyeing is carried out in such a yvay that each of these two fibers is dyed a different color. *The difference in the colors produced is due to the different affinities of the dyestuffs for the different types of fiber, as will Even though the color of one fiber may be dueto: a blend of the dyestuffs employed, the predominating color of each fiber is due to a different -which one of these fibers isused as the warp and the other is used asthe fillin and to:

figured fabrics in which the background may be composed entirely of cotton and the figure may be composed of a regenerated cellulose, orthe background may be ofthe regenerated cellulose and the figure of cotton. Stockings and other knitted wear comprising cotton fibers and fibers of a regenerated cellulose may be cross-dyed according to this invention.

To dye the cotton fibers a dyestu'ff is used which has a preferential aifinity for cotton in the presence of the regenerated cellulose q employed, and thisdyestulf is applied to the fabric in such a way that in the final product this dyestuff gives the predominating color to the cotton, although the color of the cotton may in fact be due to a blend of this dyestuff with the dyestufi' used to give the e predominating color to the regenerated cellulose. Similarly, to dye the regenerated cellulose fibers a dyestufl' is used which has a preferential affinity for the regenerated cellulose, and although the color of the re generated cellulose fibers may be due to a blend of dyestuffs, the predominating color of these fibers is produced by this dyestuif.

Not all dyestuffs give an even dyeing when applied to fabrics comprising cotton fibers and fibers of regenerated cellulose, e. g., viscose silk. Certain dyestuffs exhibit a decided preferential aflinity for one or the other type of fiber during the dyeing treatment.; In dyeing with certain dyestuffs this preferential afiinity may be emphasized by employinga higher or lower temperature during the dyeing treatment. For example,

in cross-dyeing a fabric composed of-cotton and regenerated silk fibers, it is desirable to employ a high temperature when dyeing with certain dyestuffs having a preferential aifimty for viscose silk, and a lowerte'mperaing operation.

, cided two-tone effect is from cotton.

ture in dyeing with certain dyestuffs havin a preferential aflinity for the cotton, as wil more fully appear from the examples given below.

In cross-dyeing according to this invention, it is not necessary that the dyestuffs employed should dye one of the fibers a deeper shade than the other during the dye- A dyestuf'f may be used which distributes itself more or less evenly over both types of fiber in the dye-bath, if the .d estufi is more closely held by one of bersthan the other so that when subjected to a clearing treatment, such as boiling with soap, or washing in a hot soap bath, the dyestuf'f will be sufficiently removed from one fiber to allow the production of cross-dyed effects by subsequently dyeing with a dyestuff of different color showing a preferential afiinity for the fiber retaining the least amount of the first dyestuff. For

example, a dyestuff may give a fairly even dyeing on a fabric comprising cotton and viscose silk fibers. If, on subsequently boiling the fabric with soap, or otherwise clearing, this'dyestuif is almost entirely removed from one of the fibers, e. g., the cotton, so that a cross-dyed fabric may be obtained by dyeingthe soaped fabric with a d estuff having such a preferential affinity or the cotton that on dyeing it dyes the cotton a deeper shade than the viscose silk, such a dyestuff may be used incross-dyeing because it has a preferential affinity for viscose silk.

When a separate dye-bath is used for each of the dyestuffs employed in cross-dyeing according to this invention, even though a deproduced on the fabric during the first dyelng operation, without subsequent treatment, it is often desirable to subject the fabric to a clearing operation between the two dyeing operations in order to at least partially remove the color from the fiber which it is intended should be dyed to the least extent in the first dye-bath. In general, a hot soap bath will satisfactorily clear the color from cotton and not detrimentally afiect the color on the viscose silk. Turkey red oil may be added to the soap-bath. Hydrochloric acid may be used to clear certain basic colors illustrate applications of such a clearing The examples given below- Ewample l.--I have found that certain substantive dyestuffs, for example, direct rubine B concentrated Schultz Number 313, will when combined with certain vegetable oils such as castor oil, pine oil, balsam oil, turpentine and the like to the approximate amount of about 66 of the oils, singly or in combination and 33 of the dyestufi' will form a paste that when entered into the dye machine containing sufficient water at a temperature of approximately 120 F., together with the usual amount of sodium chloride and soap forms a' dye-bath which will dye the cotton to the color and shade desired and leave the xanthate silk or viscose only slightly tinted. I have also discovered that by using wool blue R Schultz Number 188 when combined with glycerine in the approximate proportion of 66%% of the glycerine and 33 of the dyestuff will form a paste that when introduced into a dye machine containing suflicient water at a temperature of approximately 130 F together with the usual amount of sodium sulfate and boil-off oil as is used in some cases, will form a dye-bath that will dye a viscose or xanthate silk to the color and shade desired and leave the cotton only sli htly tinted. If a fabric comprising viscose si k and cotton fibers is entered into the dye-bath containing the direct rubine B concentrated and the vegetable oils, which dyes cotton, the fabric can, after having been washed to remove the surplus dye, be introduced at once into the dye-bath containing the acid dyestuff, that is, the wool blue R and the glycerine and the viscose or xanthate silk will be dyed a distinct color, thus producing the two-color or cross-dye effect which heretofore has never been accomplished with these materials.

A fabric comprising viscose silk and cotton may likewise be dyed with a direct dyestuff' and an acid dyestuff without the .use of vegetable oils or glycerine. For example, a fabric comprising cotton and viscose silk fibers after being properly washed to remove oils and after wetting may be entered into a bath of direct rubine B concentrated Schultz Number 313, and the bath held at a temperature of approximately 120 F., or lower, until the cotton is dyed. The fabric is then rinsed and entered into a bath of the proper concentration of wool blue R Schultz Number 188 and held at a temperature of approximately 130, F., until the viscose is dyed to the proper,shade.

Ewample I I .-It is known that two shades of the same color can be produced on cottonviscose silk fabrics with basic dyestuffs. Rhodamine 6G extra/Schultz Number 571, rhodamine B Schultz Number 573 and Schultz Number 571 rhodamine 6G have been used for this purpose. Nevertheless, it is new, so far as I am aware, to cross-dye cotton-viscose silk material using a basic color with a preferential a .the fabric of the surplus dyestuif and then 180 F. The goods are then run into the mai chine and given from three to five ends or dips in the dye liquor, or any number required to produce a shade of sufficient depth. The dye-bath is then run off and then the goods given 'a thorough washing in cold water.

The direct dyestuifis dissolved and added to sufficient water in the machine heated to approximatel 120 F., direct yellow S2G Schultz Num er 351 or direct rubine B concentrated Schultz Number-313 may be used. dyestufi' is entered and the goods are run in and given e. g.: three to five ends or dips for the purpose of bringing up the ,shade desired on the cotton fibers in the fabric. This dye-bath is then run off and the goodsare given a thorough rinsing to clear squeezed and dried. I

I In addition to the rhodamines the following basic dyestuifs may be used; methyl violet Schultz Number 515, Victoria blue Schultz Number 559, methylene blue Schultz Number 659, Astra phloxine F. F. extra Schultz Number 596, brilliant green crystals Schultz Number 499 and malachite green, Schultz Number 495.

Other direct. dyestuffs having a,preferential aflinity for cotton in the presence of vis-. 'cose sil may be used. Such dyestuffs include dlrect rubine B concentrated Schultz No. 313, direct yellow S2G Schultz No. 10, direct fast blue 6GL Schultz No. 456, diazo sky blue B Schultz No. 337, Pontamine diazo blue 3G Schultz No.471, diazo blue. BR Schultz No. 274, diazo blue Schultz No. 326, diazo blue 2RL Schultz No. 274, diazo blue NA Schultz No. 273, cotton fast yellow A, Schultz'No. 9, azo navy blue Ex Schultz No. 387, Cotton fast oran e 5R Schultz No. 11, aminil fast yellow A chultz" No. 9, Jenyl orange Schultz No. 11 and chloramine green B'Schultz 120.470. The direct-dyestufi' is preferably applied at a temperature in the-neighborhood of 120 F. It may be preferable to have a small amount of sodium hydroxi-de in the bath containing the direct dyestuff. Al-

though here described as applied to jiggv dyeingthe process' may at times be more advantageously. carried out in dye-becks.

After dyeing with the basic dyestuif and before applying the direct dyestulf, it may be advisable to treat the two-tone fabric in I such a wa as to clear the color from the cotton. T e desirability ofsuch a treatment is greater in certain instances than'in others.

Certain'basic dyestuffs exhibit such a preferential aflinity for viscose,. especially when dyeing light shades, that little color goes to, the cotton, and in such a-case it may not be necessary to clear the fabric between applications of the dyestuffs. Where desirable, hot soap or dilute hydrochloric acid may be used to clear the color from the cotton.

Example [Ila-Two direct dyes each of which exhibits the proper preferential af finity for a different fiber may be used tocross-dye a fabric comprising cotton and.

viscose silk vfibers. After properly conditioning the material it'is immersed in a dye-bath containing 'the dyestuff with a preferential affinity for the, viscose silk, e. naphthamine brilliant. blue LG extra Siihultz Number 877, while the dye-bath is held at a temperature of .about' 190 F., to-

boiling. The dye stains the cotton but'dyes the viscose silk a much deeper shade than the cotton. This viscose silk is dyed to the desired shade. The fabric is then prefer ably rinsed with cold water before applying the dyestuff with a preferential aifinity for the cotton. Before dyeing the cotton, it may be desirable 'to boil the goods with soap or otherwise treat them to clear the color from the cotton, and then rinse. The fabric is then .immersed in the dye-bath con-. taining a direct dyestuff such .as direct rubine B Schultz Number 313 concentrated, which has a preferential afiinity for cotton in" the presence of viscose silk. Other direct dyestufl's mentionedin connection with Ex- F. An addition of :a small 'amount of so; dium hydroxide to this latter bath gives good results. .When ,sodium hydroxide is used, a final rinsein an acid bath may be used to remove any caustic. In the absence ample II may be used. The bath iskept at a temperature of about 90 to or 120 of sodium hydroxide, the cloth, after dyeing in the second dye-bath, is merely rinsed in cold water and dried. Glaubers salt, sodium phosphate or sodium chloride may be added to either or both of the'baths to get better exhaustion of the color from the bath on to the fabric; but the addition of such salts is not necessary and 1t appears to have no appreciable effect on the cross-dye- Tnstead of naphthamine brilliant blue G Ex Schultz No. 323, diphenyl red FC Schultz No.343, primuline Schultz No. 616,

may be used. Other direct. dyestuffs which have a preferential'aflinityforjviscosesilk in the presence of'cotton and maybe; used are: Jenyl red- S'GM Schultz No. 194:,diamine fast scarlet B, Schultz No. 319, triazol brilliant sky blue 6B, Schultz No. 426, cotton grey B, Schultz No. 241, amidine fast black FF, Schultz No. 436, and Jenyl fast black GG, Schultz No. 462.

Attractive fabrics may be prepared by dyeing the viscose silk with naphthamine brilliant blue G extra and dyeing the cotton with direct rubine B concentrated, direct yellow 82G, C R cotton fast yellow A or C R cotton fast orange 5R, according to the combination of colors desired. The shade to which each fiber is dyed may be regulated in the usual manner by controlling the con centration of the dye-bath or the length of the dyeing operation, etc.

If a pink or red is desired on the viscose, diphenyl red S C may be used, and any one of the following may be used on the cotton to produce the combination of colors desired: Direct yellow SQG, cotton fast yellow A, cotton fast orange 5R, direct fast blue 6GL, and cotton fast blue 4GL.

Primuline may be used to dye the viscose a desired shade of yellow and then direct rubine B concentrated, direct fast blue 6GL or cotton fast blue 4GL may be used to produce the desired color on the cotton. Other pleasing color combinations may be obtained 'by selecting other combinations from the dyestuffs listed above.

Example lV.-A fabric comprising fibers of cotton and viscose silk may be cross-dyed usingdirect dyes with a preferential affinity for the cotton in the presence of viscose silk' and developed colors which have a preferential aifinity for viscose silk in the presence of cotton. Both dyestuifs may be applied from the same dye-bath, or two separate dyebaths may be used, in which case a clearing step may be included between the two dyeing treatments.

To illustratePr-imuline and direct. rubine B concentrated may be dissolved and added to the same dye-bath. As a specific example, in the dyelng of 100 pounds of material, four ounces of primuline and 12 ounces of direct'rubine B concentrated may be dissolved and added to 40 gallons of water. The dye-bath is brought to a temperature of approximately 140 F., and the goods are given from three to five ends or dips when jiggs are used, or a corresponding treatment may be given in a dye beck. The goods are then rinsed and the primuline is diazotized with an acid solution of nitrite. A solution of 15-25% sodium nitrite and 5-7.5% hydrochloric acid or 35%,sulfuric acid ma be used. The primuline is then develope A developer may be used which will give a desired color on viscose silk to harmonize with the color produced on the cotton. A sodium hydroxide solution of phenol used as a developer will give a yellow color. Resorcin will give orange. Naphthylamine ether N powder will give blue. If, instead of direct rubine B concentrated, direct yellow SQG is used, the cotton will be dyed yellow and red may be produced on the viscose silk by developing with betanaphthol.

Thus, by combining the two dye-baths, diazotizing and developing, two separate and distinct colors may be dyed on a fabric'composed of viscose silk and cotton from the same dye-bath.

- Instead of applying both colors from the same dye-bath, it will generally be preferable -to employ separate dye-baths. The viscose silk may be dyed first, and then the cotton. For example, a fabric composed of cotton and viscose silk threads may be wet out in cold water in the usual way and left in a roll on the dye machine. The machine is filled with water which is heated to approximately 160 F., or higher, and the developed dyestuff, after having been dissolved in a small amount of water, is poured into the machine. The dyestu'fi' is preferably added in two parts, one-half after the first end or dip, and the remaining one-half after the second end or dip, after which the goods are given as many ends as is desired to bring up the shade. As a developed dyestuff having a preferential ailinity for viscose in the presence of cotton, primuline may be selected as an example. After subjecting the cloth to the dye-bath for the desired length of time, the bath is run off and the goods are rinsed, preferably in cold water, and the primuline or other developed dyestufi' is diazotized, as explained above in connection with the application of a developed dyestuff, together with a direct dyestuff from the same bath. The dyestuif is diazotized and coupled in the usual manner. The developing bath comprising the developer is applied to the fabric after the diazotization and the developer used may be selected with a view to producing a color on the viscose silk which will properly har-' moniie with the color to be later produced on the cotton. The goods are then washed with water and it is preferable to soap the goods in a warm bath and clear as much of the developed color as possible from the cotton before applying the direct dyestuif having a preferential affinity for the cotton..

The goods are then rinsed in cold water, or may preferably be first treated in a bath which is slightly acid in order to remove any trace of alkalinity from the goods.

The d e-bath for .coloring the cotton portion of the fabric is then made up by dissolving a direct dyestuff in sufiicient water, and the goods are gven a sufiicient number of dips or ends at a temperature in the neighborhood of 120 F., to produce the color and shade desired on this part of the fabric. The direct dye stuff used may be direct yellow SQG or another of the direct dyestuffs suggested in connection with Exers known in the art. For instance, when a the cotton; diazo sky blue 3G, direct diazo blue B R, direct diaz o used for producing cross-dyed-eifects'on viscose silk. .Primuline, forlexample, may be applied to the viscose silk. After, applying the primuline at a temperature near the boiling point-pf the dye-bath, and preferably after boiling down with soap or otherwise clearing, the color may be developed and then the developed color with a preferential affinity for cotton, e. g., diazosky blue B may be'produced on the cotton, using a warm bath with a temperature in the neighborhood of 90-115" FL, or higher. Any one' of the following colors may be used to dye blue B, direct diazo blue REL direct diazo blue O, direct diazo blue NA, and diazo blue ZRL. These colors are developed by coupling with the developblue is' desired, diazo sky blue B may'be developed with betanaphthol. r

Although generally better results will be obtained by using a separate dye-bath for 7 each color, it is possible to apply both dyestuffs in one bath. After diazoti'zing, the

dyestuffs will be developed with the same developer. For example primuline may be used for giving the predominating color to the viscose silk, and diazo sky blue B for the cotton. These will be applied to the fabric with the same developer.

from the same bath at a temperature of .approximately 160 F; After rinsing, the fabric is immersed in a -diazotizing bath and then beta naphthol may be used to develop red on the viscose silk and blue on the cotton. When the two-bath method is utilized, i. e., when one color is developed before the other is applied, difi'erent developers may be employed. It is possible to first treat the ,cloth with a developed color with a preferential affinity for the viscose silk, such as primuline, clear, and then apply a developed color with preferential affinity for the cotton, and then diazotize and develop both,

Those developed colors exhibiting a preferential aflinity .for cotton, listed above in connection, with Example V, may be used. together with dyestuffs of various classes for coloring viscose silk to produce attractive cross-dyed pieces, as more fully brought out in Examples VI and VII.

vhausting agents, such as Glauber mon salt, etc, may" be used and blucstone ric may be treated with naphthamine brili liant blue G extra to color the viscosesilk in the manner described in Example 'IH. One of the other direct dyestufis listed in that example for dyeing viscose silk in the presence of cotton may be used. After clearing the dyestuff from-the cotton by boiling with soap or other suitable clearing'agent,

the cotton is dyed with a developed dyestufi having a preferential 'aifinity for the cotton,

e. g.,.diazo sky blue B, at a temperature of.

about 95110 F., and diazotized and coupled with a desired developer..

H Example VII.'A basic dyestuff having a preferential afiinity for viscose silk in the resence of cotton, may be used for dyeing the viscose silk at a temperature near the boiling point of the dye-bath, and then preferably after clearing, a developed color may Although the developed color is preferably dyed from a temperature bath it may be dyed hot.

such a way as to supply one skilled in the artwith the information necessary to crossdye textile materials composed of fibers of cotton and a regenerated cellulose.

It will thus be seen that various classes ofdye-stufi's may be used for producing the de-' sired color on either of'the'fibers and various processes may be used. Several dye stuffs may be used to produce a desired color on one fiber. The viscose si may be dyed first, then the cotton, or the reverse order may be followed, on dyestuffs showing a The foregoing examples are ct forth in preferential aflinity for cotton and viscose gether with oils, ete., as described in connection with the process of Example I. Exs salt, commay be used in the usual-manner to give a desired .overtone. Acetyl cellulose, silk, wool or other fibers, may be employed together with the regenerated cellulose and cotton, and the whole may be cross-dyed to give three or more colors.

. Other devices known to the person skilled i25 in the art may be employed in producing the cross-dyed textile materials covered by this invention.

The dyestuffs and processes listed above are illustrative of this invention and the in- 5 Example VI.A cotton-viscose silk fabvention is not to be considered as limited stufi selected from the group'consistin i thereto, but is to be construed as defined in the following claims. I claim; I

1. The process of cross-dyeing a cotton-- regenerated cellulose textile fabric which comprises subjecting the fabric at a temperature near the boiling point of the dye-bath to a dyeing treatment with a dyestufi' selected from the group consisting of Schultz Numbers 323194343616- -319-426 241436 and 462, having a preferential afiinity for the regenerated cellulose in the presence of the cotton and thereafter subjecting the fabric at a lower temperature to a dyeing treatment with a dyestuff selected from the group consisting of Schultz Numbers 313 1O 326--273-471-2749 337 11 4564"70, having a preferential affinity for the cotton in the presence of the regenerated cellulose.

2. The process of cross-dyeing a cottonregenerated cellulose textile fabric which comprises subjecting the material at a temperature near the boiling point of the dyebath to a dyeing treatment with a dyestuif selected from the group consisting of Schultz Numbers 323343-194-616319426 241-436 and 462, having a preferential affinity for the regenerated cellulose in the presence of the cotton, washing with a hot soap solution, and thereafter subjecting the fabricata lowertemperature to a dyeing treatment with a dyestuff selected from the group consisting of Schultz Numbers 313 10 326 -273471' 27491l456337 and 47 0 having a preferential affinity for the cotton in the presence of the regenerated cel lulose.

3. The method of cross-dyeing a textile fabric comprising fibers of cotton and a regenerated cellulose of the viscose type, which comprises subjecting the fabric to the action of a direct dyestuff selected from the group consisting of Schultz Numbers 323194 343-6163l9426241.436 and 462, with a preferential aflinity for one of these two fibers in the presence of the other and subjecting 'the fabric to the action of a dyeof Schultz 'Numbers '313- -103262734 1- 2749- -11'456337 and 470 having a preferential afiinityfor the other of the two bers'in the presence of theother fiber.

4. The method of cross-dyeing a textile fabric comprising fibers, of cotton andia regenerated cellulose whichcomprises subjecting the fabric at ja temperature iii the neighborhood of to 1209 F., to the action of a direct 'dyestuif selected from the' group consisting of Schultz 'Numbers 31310'326-- a preferential affinity for the regenerated cellulose in the presence of the cotton.

5. The method of cross-dyeing a textile fabric comprising both cotton and viscose silk which comprises subjecting the fabric to the action of a direct dyestuff selected from the group consisting of Schultz Numbers 323-343- 194616319426-241-- 436 and 462 with a preferential aflinity for viscose silk in the presence of cotton at a temperature near the boiling point of the dye-bath and subjecting the fabric to the action of a direct dyestuff selected from the group consisting of Schultz Numbers 313 10 326 273 47 1 274r-9- 11 45e 337 and 47 0 with a preferential afiinity for cotton in the presence of viscose silk at a lower temperature.

6. The method of cross-dyeing a textile fabric comprising both cotton'and viscose silk which comprises subjecting the fabric to the action of a direct dyestuff selected from the group consisting of Schultz Numbers 323 343 1-946l6319426241436 and 462 with a preferential affinity for viscose silk in the presence of the cotton at a temperature near the boiling point of the dye-bath, washing with a hot soap solution to partially clear the color from the cotton and thereafter subjecting the fabric to the action of a direct dyestuif selected from the group consisting of Schultz Numbers 313- 10 326 2734' 71274911456-337 and 470 with a preferential afiinity for the cotton in the presence of viscose silk at a lower temperature. I

In testimony whereof I afiix my signature.

/ ARTHUR S. ROBERTS.

273-471 274. 9-11-4.5e 337 and 470 and also subjecting the material to the action of a dy'estuff selected from the group consisting of. Schultz Numbers 323343 194616'-319- 426-24l-436 and 462 with 

